WO2003035642A1 - Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation - Google Patents

Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation Download PDF

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Publication number
WO2003035642A1
WO2003035642A1 PCT/IN2001/000190 IN0100190W WO03035642A1 WO 2003035642 A1 WO2003035642 A1 WO 2003035642A1 IN 0100190 W IN0100190 W IN 0100190W WO 03035642 A1 WO03035642 A1 WO 03035642A1
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WIPO (PCT)
Prior art keywords
alkyl
hydrogen
formula
compound
alkoxy
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PCT/IN2001/000190
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English (en)
Inventor
Shrojlal Mohitkumar Desai
Raj Pal Singh
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Council Of Scientific And Industrial Research
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Priority to PCT/IN2001/000190 priority Critical patent/WO2003035642A1/fr
Priority to EP01983761A priority patent/EP1444222A1/fr
Publication of WO2003035642A1 publication Critical patent/WO2003035642A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to invention relates to a novel photo-stabilizer of the general formula (I):
  • Ri is hydrogen, halogen, Ci to C ⁇ 2 alkyl, alkoxy (linear and branched)
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl
  • R 3 is hydrogen, C ⁇ -C 4 alkyl
  • R is methyl or ethyl
  • R 5 is Ci-C 8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl
  • X is O, NH, Ci-C 8 alkyloxy and alkylamino (linear or branched). More particularly, the present invention relates to the said compound of formula I prepared using bromo derivative of Tinuvin P of the general formula (II).
  • R x is hydrogen, halogen, Ci to C 12 alkyl, alkoxy (linear and branched), R 2 is hydrogen, C ⁇ -C 8 allcyl, cyclopentyl, cyclohexyl or cumyl, as disclosed in our co-pending Patent application No. 09/749, 277 by reacting with a compound of the formula (IV).
  • R 3 is hydrogen, C ⁇ -C 4 alkyl, R 4 is methyl, ethyl, R 5 is C C 8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl, X is OH, NH 2 , C x -C 8 alkyloxy and alkylamino (linear or branched).
  • the present invention also relates to a process for the synthesis of a novel photo- stabilizer of the general formula (I):
  • Ri is hydrogen, halogen, Ci to C1 2 alkyl, alkoxy (linear and branched)
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl
  • R 3 is hydrogen, C ⁇ -C alkyl
  • R 4 is methyl or ethyl
  • R 5 is C ⁇ -C 8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl
  • X is O, NH, Ci-Cs alkyloxy and alkylamino (linear or branched). More particularly, the present invention relates to the preparation of said compound using bromo derivative of Tinuvin P of the general formula (II).
  • R ⁇ is hydrogen, halogen, Ci to C 12 alkyl, alkoxy (linear and branched), R 2 is hydrogen, C ⁇ -C 8 allcyl, cyclopentyl, cyclohexyl or cumyl, as disclosed in our co-pending Patent application No. 09/749, 277 by reacting with a compound of the formula (IV).
  • R 3 is hydrogen, C1-C4 alkyl, R4 is methyl, ethyl, R 5 is Ci-Cs alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl, X is OH, NH 2 , C ⁇ -C 8 alkyloxy and alkylamino (linear or branched).
  • Polymers have replaced metals glass, ceramics and papers in packaging, automobiles, building construction, electronics, electrical equipment, furniture, pipes and heavy industrial equipment.
  • plastics In a nutshell, from agriculture to transport and aerospace to food packaging, the use of plastics has become an integral part of our daily life.
  • HALS Hindered amine light stabilizer
  • benzotriazole based UV absorbers are known to work in synergism and there is no literature on the synthesis of the coupled derivatives of HALS and UV absorbers.
  • the main object of the invention is to provide a process for the preparation of novel Tinuvin P- Hlashd Amine Light Stabilizer (TP -HALS) derivatives, which can fulfil the above mentioned prerequisites.
  • TP -HALS Tinuvin P- Hlashd Amine Light Stabilizer
  • this class of combination of HALS and benzoriazole are known to be compatible with polyolefins, polycarbonate, polystyrene and diene - elastomers and can even be added in an additive proportion to obtain desired photo- stability of various other polymers.
  • the present invention provides a novel Tinuvin P-Hlashd Amine Light Stabilizer derivative of the general formula (I):
  • Ri is hydrogen, halogen, Ci to C 12 alkyl, alkoxy (linear and branched),
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl
  • R 3 is hydrogen, C 1 -C 4 alkyl
  • R 4 is methyl or ethyl
  • R 5 is C ⁇ -C 8 alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl
  • X is O
  • the present invention also provides a process for preparation a novel Tinuvin P-
  • Rn is hydrogen, halogen, Ci to C 12 alkyl, alkoxy (linear and branched)
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl, with an organic base in a dry organic solvent under inert condition, agitating it initially for a period of 20-30 minutes followed by addition of an hydroxy protecting group and stirring the reaction mixture for 10- 14 min under inert atmosphere, followed by evaporating the organic solvent and drying the residue, subsequently dissolving the residue in a low boiling organic solvent followed by filtering the insoluble mass and evaporating the solvent to obtain a compound having general formula (III)
  • Ri is hydrogen, halogen, Ci to C ⁇ 2 alkyl, alkoxy (linear and branched)
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl
  • Y is tertbutyldimethylsilyl, tertbutyldiphenylsilyl, dimethylthexylsilyl, benzoyl, benzyl, and acetyl, dissolving compound of formula (III) in a dry organic solvent under inert condition and simultaneously dissolving compound of formula (IV)
  • Ri is hydrogen, halogen, Ci to C ⁇ 2 alkyl, alkoxy (linear and branched)
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, cyclopentyl, cyclohexyl or cumyl
  • R 3 is hydrogen, C1-C4 alkyl
  • R4 is methyl or ethyl
  • R 5 is Ci-Cs alkyl, alkyl phenyl, alkoxy, acyl, cycloalkyl and allyl
  • X is O, NH, C ⁇ -C 8 alkyloxy and alkylamino (linear or branched)
  • Y is tertbutyldimethylsilyl, tertbutyldiphenylsilyl, dimethylthexylsilyl, benzoyl, benzyl, and acetyl, taking the compound (V) with a hydroxy deprotecting reagent and stirring the reaction mixture at room temperature for 1-3 hrs followed by addition
  • the organic solvent used for dissolving the compound of formula (II) is selected from the group consisting of pyridine, dichloromethane, dimethylformamide, tetrahydrofuran, acetonitrile and 1,4-dioxane.
  • the base used to react with compound of formula (II) is selected from the group consisting of imidazole, pyridine, 2,6-lutidine, trimethyl amine, mercaptobenzoxazole and alkyl substituted pyridine.
  • the hydroxy protecting group is selected from the group consisting of tert-butyldimethylsilyl chloride, tert-butyl-di-phenylsilyl chloride, dimethylthexylsilyl chloride, acetyl chloride, benzoyl chloride, benzyl bromide, benzoic acid, acetic anyhydride and acetic acid.
  • the catalyst used is selected from dimethyl aminopyridine, diethyl aminopyridine, dimethyl aniline, dicyclohexyl carbodimide and hydroxy benzotriazole.
  • the organic solvent used for dissolving the crude mass is selected from the group consisting of dichloromethane, chloroform, acetone, diethyl ether and benzene.
  • the solvent used to dissolve compound of formula (III) is selected from the group consisting of dimethylformamide, tetrahydrofuran, acetonitrile, 1,4- dioxane and dichloromethane.
  • the hindered amine having general formula (IV) added to react with compound (III) is selected from the group consisting of 1,2,2,6,6- pentamethyl-4- aminopiperidine, 1 ,2,2,6,6-pentamethyl-4-piperidinol, 1 ,2,2,4,6,6-hexamethyl-4- aminopiperidine, 1,2,2,6,6- pentamethyl-4-ethylaminopiperidine and its derivatives.
  • the metal hydride is selected from sodium hydride and potassium hydride.
  • the solvent used for extracting the product from the aqueous medium is selected from the group consisting of dichloromethane, dichloroethane, ethyl acetate, diethyl ether, benzene and n-hexane.
  • hydroxy deprotecting agent for deprotecting the compound of formula (V) is selected from the group consisting of tetrabutyl ammonium fluoride, boron triflouride, boron trichloride, boron tribromide, aluminum chloride, sodium bicarbonate, aqueous ammonia, hydrochloric acid, lithium chloride and lithium aluminum hydride.
  • the solvent used for extracting the product from the aqueous medium is selected from the group consisting of dichloromethane, dichloroethane, ethyl acetate, diethyl ether, benzene and n-hexane.
  • the inert gas is selected from Nitrogen and Argon.
  • the inorganic base used to neutralize the solvent fraction containing the product is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium bicarbonate and potassium carbonate.
  • HALS monomers and some of its derivatives may be prepared by any of the methods that are known in the art including those disclosed in Patents No. JP 53015385 28 (July 1978), Swiss CH 610898 (15 May 1979), Swiss CH 605927 (Oct 1978), Brit. GB 1492494 (Nov 1977) and Literature: T. Tsuchiya and H. Sashida, Heterocycles, 14, 1925-8 (1980).
  • HALS namely 2,2,6,6-tetramethyl piperidine and 2,2,6,6 - tetramethyl-4-piperidinol may be prepared by synthetic route disclosed by W. B. Lutz, S. Lazams and R. I.
  • hydroxy benzotriazoles can be prepared by any of the above mentioned methods, disclosed in the patents and literature. All these patents and literature are incorporated herein by reference.
  • the present invention relates to a novel photo-stabilizer; TP-HALS a HALS coupled to an UV absorber and their derivatives. This class of compounds is added to the polymers in order to improve their photo-stability and in turn their life span. They can also be used to obtain photo-stable coatings and paints for out-door applications.
  • HALS and benzotriazoles are found to be compatible with polyolefins, polycarbonate, and a variety of diene elastomers.
  • the novel photo-stabilizer synthesized by the process of the invention bears two different active sites in the same molecule, which are known to work in synergism.
  • the hindered amine site acts as a radical scavenger and the bezotriazole site acts as an UV absorber, thus avoiding the addition of two different additives to the polymer.
  • coupling these two different photo- stabilizers not only increase the active sites but also help in increasing the overall molecular weight of the stabilizer, thus decreasing the possibility of its loss due to evaporation, migration /leaching and extraction.
  • These additives have even found applications in a variety of polymers used for food storage, consumer care products and pharmaceuticals, preserving the packaging content from the detrimental effect of high heat and harmful radiation.
  • the literature also shows their agricultural applications.
  • the deterioration of polymeric materials is an inevitable phenomenon and it occurs mainly due to their exposure to the UN portion of sunlight reaching the earth's surface.
  • the net result of degradation is the loss in the molecular weight and macroscopic physical properties.
  • photo-stabilizers In order to avoid this loss different types of photo-stabilizers have been devised that protect the polymeric substrate from detrimental effect of light.
  • the compatible and mobile light stabilizers usually prove to be the best choice to attain the desired photostability. Most of these stabilizers are commercially available and are successfully employed, single and/or in combination with other stabilizers for the polymer stabilization.
  • researchers have even attempted to study the combined effect of screeners, quenchers, ultraviolet absorbers and thermal stabilizers.
  • HALS ine light stabilizer
  • UN absorber of the invention overcomes the prior art disadvantages listed above.
  • This invention provides a novel photo-stabilizer: Tinuvin P -Hindered Amine Light Stabilizer (TP-HALS) and its derivatives.
  • TP-HALS Tinuvin P -Hindered Amine Light Stabilizer
  • the derivatives of conventional HALS and benzotriazoles have enhanced photo-stabilization effect, and are useful as additives in a variety of polymers used for food storage, consumer care products (viz. sunscreen/ anti-aging lotions) and pharmaceuticals, preserving the packaging content intact.
  • This compound was synthesized strictly under dry and inert reaction conditions.
  • This reaction mixture was agitated for almost 60 rnin and then cooled to 4-8°C.
  • the contents of the first RB was added gradually over a period of 30- 60 min.
  • This reaction mixture was further agitated for 2-4 hrs followed by refluxing the same for a period of 2-4 hrs.
  • the contents of the RB were cooled to room temperature and further agitated for 4-6 hrs at room temperature.
  • the solvent in the RB was evaporated under reduced pressure and the solid mass in the RB was dissolved in 15 mL water and repeatedly extracted with dichloromethane (4 x 10 mL).
  • the process comprises of commonly available organic reagents and employs mild reaction conditions.

Abstract

La présente invention porte sur un nouveau photo-stabilisant représenté par la formule générale (I), dans laquelle R1 représente hydrogène, halogène, alkyle C1-C12, alcoxy (à chaîne linéaire ou ramifiée) ; R2 représente hydrogène, alkyle C1-C8, cyclopentyle, cyclohexyle ou cumyle ; R3 représente hydrogène, alkyle C1-C4 ; R4 représente méthyle ou éthyle ; R5 représente alkyle C1-C8 , alkyle phényle, alcoxy, acyle, cycloalkyle et allyle ; X représente O, NH, alkyloxy C1-C8 et alkylamino (à chaîne linéaire ou ramifiée).
PCT/IN2001/000190 2001-10-23 2001-10-23 Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation WO2003035642A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/IN2001/000190 WO2003035642A1 (fr) 2001-10-23 2001-10-23 Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation
EP01983761A EP1444222A1 (fr) 2001-10-23 2001-10-23 Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation

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PCT/IN2001/000190 WO2003035642A1 (fr) 2001-10-23 2001-10-23 Photo-stabilisant tinuvin p a amine inhibee, ses derives et son procede de preparation

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005066141A1 (fr) * 2003-12-25 2005-07-21 Council Of Scientific & Industrial Research Antiozonants a la base d'absorbeurs d'uv benzotriazoles fonctionnalises et leur production
WO2007036948A1 (fr) * 2005-09-30 2007-04-05 Council Of Scientific & Industrial Research Nouvel absorbeur d'uv de type benzotriazole substitué par un mercaptobenzimidazole et procédé pour la préparation de celui-ci

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE106492C (fr) *
DE2258752A1 (de) * 1971-11-30 1973-06-07 Ciba Geigy Ag Neue piperidin-derivate
DE2352658A1 (de) * 1972-10-21 1974-04-25 Ciba Geigy Ag Piperidinderivate als stabilisatoren
DE2500313A1 (de) * 1974-01-12 1975-07-17 Ciba Geigy Ag Chemische verbindungen
DE2642461A1 (de) * 1976-09-21 1978-03-30 Bayer Ag Permanent stabilisierte polymere
US4709041A (en) * 1981-11-16 1987-11-24 Polaroid Corporation 2-(formylphenyl) benzotriazole intermediates
US5021478A (en) * 1989-03-21 1991-06-04 Ciba-Geigy Corporation Compounds containing both UV-absorber and 1-hydrocarbyloxy hindered amine moieties and stabilized compositions
US5362881A (en) * 1993-05-27 1994-11-08 Fairmount Chemical Company, Inc. Coupled benzotriazole and benzophenone UV absorbers
JPH11209392A (ja) * 1998-01-27 1999-08-03 Nippon Paper Industries Co Ltd ベンゾトリアゾール誘導体およびそれを用いた感熱記録体
US6284895B1 (en) * 2000-12-27 2001-09-04 Council Of Scientific And Industrial Research Bromo-functionalized benzotriazole UV absorbers

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE106492C (fr) *
DE2258752A1 (de) * 1971-11-30 1973-06-07 Ciba Geigy Ag Neue piperidin-derivate
DE2352658A1 (de) * 1972-10-21 1974-04-25 Ciba Geigy Ag Piperidinderivate als stabilisatoren
DE2500313A1 (de) * 1974-01-12 1975-07-17 Ciba Geigy Ag Chemische verbindungen
DE2642461A1 (de) * 1976-09-21 1978-03-30 Bayer Ag Permanent stabilisierte polymere
US4709041A (en) * 1981-11-16 1987-11-24 Polaroid Corporation 2-(formylphenyl) benzotriazole intermediates
US5021478A (en) * 1989-03-21 1991-06-04 Ciba-Geigy Corporation Compounds containing both UV-absorber and 1-hydrocarbyloxy hindered amine moieties and stabilized compositions
US5362881A (en) * 1993-05-27 1994-11-08 Fairmount Chemical Company, Inc. Coupled benzotriazole and benzophenone UV absorbers
JPH11209392A (ja) * 1998-01-27 1999-08-03 Nippon Paper Industries Co Ltd ベンゾトリアゾール誘導体およびそれを用いた感熱記録体
US6284895B1 (en) * 2000-12-27 2001-09-04 Council Of Scientific And Industrial Research Bromo-functionalized benzotriazole UV absorbers

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Title
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CYGLER M. ET AL: "Conformation of the piperidine ring", JOURNAL OF MOLECULAR STRUCTURE, vol. 68, 1980, NL, pages 161-171, XP002198903 *
GAN H. ET AL: "A sterically controlled recyclable system: Reversible photredox reactions between anthraquinone and hindered tertiary amines", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 115, 1993, USA, pages 8031-8037, XP002198901 *
LUTZ W.B. ET AL: "New derivatives of 2,2,6,6-tetramethylpiperidine", JOURNAL OF ORGANIC CHEMISTRY, vol. 27, 1962, USA, pages 1695-1703, XP002198902 *
ORTHNER L.: "Zur raumchemie des dreiwertigen stickstoffs und von N-heterocyclen", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 456, 1927, DE, pages 225-252, XP001070750 *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 13 30 November 1999 (1999-11-30) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005066141A1 (fr) * 2003-12-25 2005-07-21 Council Of Scientific & Industrial Research Antiozonants a la base d'absorbeurs d'uv benzotriazoles fonctionnalises et leur production
WO2007036948A1 (fr) * 2005-09-30 2007-04-05 Council Of Scientific & Industrial Research Nouvel absorbeur d'uv de type benzotriazole substitué par un mercaptobenzimidazole et procédé pour la préparation de celui-ci

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